WO1999054362A1 - Procede et dispositif pour la production en continu de polymeres - Google Patents

Procede et dispositif pour la production en continu de polymeres Download PDF

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Publication number
WO1999054362A1
WO1999054362A1 PCT/EP1999/001734 EP9901734W WO9954362A1 WO 1999054362 A1 WO1999054362 A1 WO 1999054362A1 EP 9901734 W EP9901734 W EP 9901734W WO 9954362 A1 WO9954362 A1 WO 9954362A1
Authority
WO
WIPO (PCT)
Prior art keywords
micromixer
educt
solvent
tubular reactor
polymers
Prior art date
Application number
PCT/EP1999/001734
Other languages
German (de)
English (en)
Inventor
Detlev Pysall
Olaf Wachsen
Thomas Bayer
Stefan Wulf
Original Assignee
Axiva Gmbh
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Axiva Gmbh filed Critical Axiva Gmbh
Priority to AU34135/99A priority Critical patent/AU3413599A/en
Priority to AT99915632T priority patent/ATE302796T1/de
Priority to JP2000544700A priority patent/JP4410416B2/ja
Priority to US09/673,156 priority patent/US6555629B1/en
Priority to EP99915632A priority patent/EP1086143B1/fr
Priority to DE59912468T priority patent/DE59912468D1/de
Publication of WO1999054362A1 publication Critical patent/WO1999054362A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F25/00—Flow mixers; Mixers for falling materials, e.g. solid particles
    • B01F25/30—Injector mixers
    • B01F25/31—Injector mixers in conduits or tubes through which the main component flows
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F33/00—Other mixers; Mixing plants; Combinations of mixers
    • B01F33/30—Micromixers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/0093—Microreactors, e.g. miniaturised or microfabricated reactors
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/24—Stationary reactors without moving elements inside
    • B01J19/2415—Tubular reactors
    • B01J19/242—Tubular reactors in series
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F25/00—Flow mixers; Mixers for falling materials, e.g. solid particles
    • B01F2025/91—Direction of flow or arrangement of feed and discharge openings
    • B01F2025/917—Laminar or parallel flow, i.e. every point of the flow moves in layers which do not intermix
    • B01F2025/9171—Parallel flow, i.e. every point of the flow moves in parallel layers where intermixing can occur by diffusion or which do not intermix; Focusing, i.e. compressing parallel layers without intermixing them
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F35/00—Accessories for mixers; Auxiliary operations or auxiliary devices; Parts or details of general application
    • B01F35/90—Heating or cooling systems
    • B01F2035/99—Heating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F2101/00—Mixing characterised by the nature of the mixed materials or by the application field
    • B01F2101/2805—Mixing plastics, polymer material ingredients, monomers or oligomers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00781—Aspects relating to microreactors
    • B01J2219/00889—Mixing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/0002—Condition, form or state of moulded material or of the material to be shaped monomers or prepolymers

Definitions

  • the invention relates to a method and a device for the continuous production of polymers, in which at least two reactants (starting materials) are passed through a micromixer and brought together and mixed together.
  • the reactants are, for example, one or more liquid or dissolved monomers and one or more initiators.
  • a so-called micro-structure lamella mixer with at least one mixing chamber and an upstream guide component for the supply of the fluids to be mixed to the mixing chamber is used for the mixing.
  • the guide component can be composed of a plurality of plate-like elements which are layered one above the other and which are crossed by channels which run obliquely or transversely to the longitudinal axis of the micromixer. The channels of adjacent elements cross without contact and open into the mixing chamber.
  • Another way of designing a micromixer is to use a parallel one 2
  • the fluids to be mixed flow into the mixer from opposite directions and, when mixed, exit the mixer chamber perpendicularly thereto.
  • the reactants are brought into intimate contact with one another by the mixer, i.e. well mixed together.
  • the quality of the mixing and the influence of the mixing organ on the yield of the desired product depends to a large extent on the ratio of the chemical reaction rates given by the reaction kinetics to the mixing rate. In the case of chemically slow reactions, these generally run much more slowly than the mixing. If the chemical reaction rates and the mixing rate are of the same order of magnitude, complex interactions occur between the kinetics of the reactions and the local mixing behavior determined by the turbulence in the reactor used and in the mixing element, which is generally a micromixer. If the chemical reaction rates are significantly faster than the mixing rate, the reaction rates and the yields are essentially determined by the mixing, i.e. determined by the local, time-dependent speed and concentration field of the reactants.
  • This high molecular weight fraction can result, among other things, from an initially poor mixing of monomers and initiator, since a local deficit of initiator can lead to the formation of macromolecules with a very high degree of polymerization, which are known to occur in the case of radical polymerization within a time of less than one second .
  • These high molecular weight fractions lead to a significant broadening of the molecular weight distribution up to bimodal molecular weight distributions. As a result, undesirable deposits occur in the reactor system.
  • the precipitation of the insoluble molecules from the solution is known to be promoted by solid surfaces such as reactor walls, internals, etc.
  • tubular reactors which are often equipped with static mixers to intensify the mixing processes and heat transfer, there is a large and therefore unfavorable surface-volume ratio.
  • a batch stirred tank reactor with comparable capacity, it is assumed that there is a greater likelihood of deposit formation in the reactor system, which in the case of the continuously operated tubular reactor can lead to blockage of the system and preclude continuous operation.
  • the generally small amounts of polymer with high molar masses in the product mixture can be sufficient to add a tubular reactor since the process is operated over very long times. If, in the case of the tubular reactor at the beginning of the reactor, there is poor homogenization of the reaction mixture over a system-dependent mixing section, an intensive deposit formation can occur, particularly in this area.
  • the acrylate-based monomers can be, for example, copolymers as described in DE-A 40 27 594. These copolymers are potentially based on alkyl and functionalized alkyl esters of ⁇ , ⁇ -ethylenically unsaturated carboxylic acids and optionally copolymerizable vinyl monomers. Another monomer is styrene, for example. 4
  • a process for continuous anionic polymerization is known from EP 0 749 987 A1.
  • the monomer system consists of at least one (meth) acrylic acid monomer.
  • the initiator consists of metal organyls, such as are used for anionic polymerization. Since such reactions are very fast reactions which lead to complete conversion within 0.2 to 0.3 seconds, an adiabatic tubular reactor with an upstream micromixer was developed for continuous reaction control.
  • the micromixer is a turbulent mixing tangential flow mixer.
  • the residence time in the mixer is approx. 0.05 seconds.
  • the starting materials (monomers, solvents and initiator) are cooled down to -14 to -40 ° C. before being fed into the mixer in order to avoid a start of the reaction in the mixer.
  • the reaction takes place in the tubular reactor.
  • the adiabatic reaction leads to a final temperature of 44 ° C to 91 ° C.
  • the object of the invention is to provide a method and a device for the continuous production of free radical solution polymers, in which a blockage or occupation of the reactor system is largely avoided and the device for longer periods without Interruption can be operated.
  • This object is achieved according to the invention by a method of the type described in the introduction in such a way that the educts are preheated before entering the micromixer to such an extent that they reach a required reaction temperature after entering the micromixer, in which they are obtained by diffusion and / or Turbulence are mixed in such a way that the formation of bimodal molecular weight distributions or high molecular weight fractions does not occur and that the monomer reactants are polymerized in a tubular reactor downstream of the micromixer.
  • the mixing takes place immediately, ie that the mixing time is less than the reaction time to form a single polymer chain.
  • Preferred mixing times Depending on the reaction time, 5 range from one second to spontaneous mixing. Typical reaction times are familiar to the person skilled in the art and, depending on the reaction type and temperature, are in the range from milliseconds to a few seconds.
  • the required reaction temperature can be reached immediately after entering the micromixer by preheating.
  • the one educt of monomers based on acrylate with a styrene additive and a solvent is passed through a first heated heat exchanger.
  • the other starting material from a radical initiator and optionally a solvent is passed through a second heated heat exchanger.
  • the educt from monomer solvent and the educt from initiator solvent are fed into the micromixer in a mixing ratio of 1: 1 to 10: 1, in particular 9: 1.
  • the device for the continuous production of polymers with storage tanks for the reactants, dosing and control devices, filters and with or without a premixer is characterized in that both the storage tanks for the educt from monomers and optionally solvents and the storage tanks for the educt Initiator and optionally solvent, a heated heat exchanger is connected downstream, that each of the two heat exchangers is connected via lines to the micromixer and that the micromixer is connected to a tubular reactor which is connected to a discharge container for the solution polymers.
  • a heated heat exchanger is connected downstream, that each of the two heat exchangers is connected via lines to the micromixer and that the micromixer is connected to a tubular reactor which is connected to a discharge container for the solution polymers.
  • the process according to the invention differs from the known process from EP 0 749 987 A1 in that the known process relates to anionic polymerizations, while the process according to the invention relates to radical polymerizations. Different initiator systems are therefore used.
  • the known method is also based on an adiabatic temperature control of the tubular reactor.
  • the new process can include controlled temperature control, with defined, adjustable temperatures, which is favorable for the reaction control of the radical polymerization.
  • the starting materials are fed to the micromixer at -13 ° C to -40 ° C. The heating takes place through the heat of reaction formed in the subsequent polymerization.
  • the feed streams are preheated such that after mixing, preferably immediately after entry, an initial temperature of e.g. 120 ° C (depending on the type of reaction). Excess heat of reaction, which would lead to heating of the reaction mixture, can be dissipated from the system using conventional cooling. Due to the different starting temperatures in the known and in the new process according to the invention, in the known process the reaction takes place exclusively in the tubular reactor which takes place downstream of the micromixer. In the new process, the reaction can already take place in the micromixer. In the known method, the micromixer is described by an exclusively turbulent mixing tangential flow mixer. The new method preferably uses micromixers with a lamella structure, which mix by diffusion and / or turbulence.
  • a micromixer is used in the invention.
  • the two educt streams to be mixed are brought together via very fine lamellar channels in such a way that already at
  • the educts are mixed in the micro range 7 is present. Due to the design, such a micromixer has extremely small channels which lead to an extremely high surface-to-volume ratio, as a result of which the likelihood of the formation of deposits in the mixing system and consequently the likelihood of the mixer becoming blocked should increase sharply. Surprisingly, however, the formation of a high molecular weight fraction can be avoided by the very good mixing of the starting materials, so that no insoluble high molecular weight fraction is formed in the molecular weight distribution and, despite the extremely large surface-volume ratio, no deposit formation occurs in the reactor system.
  • FIG. 2 shows a plan view of a micromixer used in the device according to the invention as an example
  • FIG 3 is a plan view of a mixing unit of the micromixer with a number of channels on each feed side
  • Fig. 1 shows the flow diagram of a device 1 or a plant for the production of solution polymers.
  • Starting materials are a monomer-solvent mixture that is stored in storage containers 2 and 3 and an initiator-solvent mixture that is contained in storage containers 4 and 5.
  • the storage container 2 contains a mixer, the stirrer is set in rotation by a motor M, via a metering and regulating device 6, the storage container 2 is connected to the storage container 3, which, like the 8th
  • Storage container 4 can be charged with nitrogen, for example, in a manner not shown.
  • the monomer-solvent mixture flows from the storage container 3 via a line in which a filter 8 is installed, which filters out any impurities from the mixture, into a heated heat exchanger 11 and from there via a heated line 27 and a filter 17 into one Micromixer 18.
  • the micromixer 18 is a micromixer of various embodiments available on the market.
  • the initiator-solvent mixture is passed through a heated heat exchanger 12 through filters 9 and 29 from the reservoir 4.
  • the further reservoir 5 for the initiator-solvent mixture is connected to the line via a filter 10, a metering and regulating device 7, in which the filters 9 and 29 are arranged.
  • the heat exchanger 12 is also connected to the micromixer 18 via a heated line 28.
  • a closed circuit is provided for the heating medium for heating the line 27, in which the heating medium is removed at the outlet of the line 27 and is returned to the beginning of the line 27 via a premixer 19, the micromixer 18 and a metering and regulating device 13.
  • a heating device 15 heats the heating medium flowing through the closed circuit.
  • the heating of line 28 takes place in a similar manner, in that at the end of line 28 the heating medium is returned to the beginning of line 28 via a metering and regulating device 14.
  • the heating medium in this closed circuit is heated by a heating device 16.
  • the heat exchangers 11, 12 are preheated to a temperature from below the reaction temperature to the reaction temperature. For example, this temperature is in the range of 50 to 180 ° C.
  • a tube reactor 20 which, for example, consists of three separately heatable tubes 21, 22 and 23, each of which has a length of 1 m, for example.
  • the heated tubes 21, 22, 23 are completely equipped with mixers, with Kenics, for example, in the tubes 21 and 22. 9
  • the tubes 21, 22, 23 are preferably equipped with static mixers, but it is also possible to have the tubes work without a mixer.
  • the tubes 21 and 22 have, for example, a nominal diameter of 10 mm, while the tube 23 has a nominal diameter of 20 mm.
  • the nominal diameters of the tubes of the tube reactor 20 can be freely selected and are determined according to the desired throughput of solution polymers.
  • a Sulzer SMX mixer, for example, is also provided as the premixer 19, which can have a nominal diameter of 5 mm. With the pipe diameters specified, the total volume of the three pipes 21, 22 and 23 of the pipe reactor 20 is approximately 0.5 I.
  • tubular reactor 20 instead of the tubular reactor 20, there is also the possibility that other reactors are used in the post-reaction section, which contain heated mixers, for example.
  • the monomer-solvent mixture and the initiator-solvent mixture are fed into the micromixer in a defined mixing ratio of 1: 1 to 10: 1, in particular 9: 1.
  • These two reactants also referred to as educts, are passed through the micromixer and brought together in a mixing and reaction space of the micromixer.
  • the upstream temperature-controlled heat exchangers 11 and 12 heat the two starting materials to such an extent that the required reaction temperature of, for example, 60 ° to 180 ° C. is reached immediately during the mixing process in the micromixer 18.
  • the reaction temperature depends on the respective reactants and is not limited to the above range.
  • the two reactants are polymerized in the downstream tube reactor 20.
  • the molar masses, the conversion and the viscosity for a given monomer mixture are adjusted via the respective initiator or its concentration and via the temperature control of the tube reactor section and the residence time of the reactants in the tube reactor 20 .
  • One reactant is, for example, an educt of monomers based on acrylate, with or without the addition of styrene, and a solvent.
  • the other 10 is, for example, an educt of monomers based on acrylate, with or without the addition of styrene, and a solvent.
  • Reaction partner consists of one or more radical initiators and a solvent.
  • the tubular reactor 20 is connected via discharge lines 25 and 26 to a discharge container 24 for the solution polymers.
  • a control valve 32, 33 is arranged in each of the discharge lines 25, 26, by means of which the operating pressure in the tubular reactor 20 can be controlled. With the help of the control valves 32, 33, the operating pressure in the reactor section after the tubular reactor 20 is regulated, for example, in the range from 2 ⁇ 10 5 Pa to 5 ⁇ 10 6 Pa in order to avoid boiling of the reaction mixture in the tubular reactor.
  • the discharge lines 25 and 26 are cooled.
  • the discharge container 24 is a stirred container, the stirrer of which is rotated by a motor M.
  • FIG. 2 shows a perspective top view of a micromixer 18, which is a static micromixer known per se.
  • the micromixer 18 comprises a micromixer arrangement with a number of mixing units 30 which are arranged in a star shape.
  • the number of channels 31, cf. 3, per mixing unit is 2 x 16 to 2 x 18.
  • the reactants or starting materials to be mixed with one another are brought together via the lamellar channels 31 in such a way that when the reaction streams occur, the starting materials are mixed in the micro range .
  • the channels in the micromixer 18 have an extremely high surface-to-volume ratio, which usually greatly increases the likelihood of the formation of deposits in the mixer system and, consequently, the likelihood of the micromixer 18 becoming blocked, the very good mixing of the starting materials results in the formation of a high molecular weight Part of the molecular weight distribution largely avoided. In spite of the extremely large surface-volume ratio, there is no formation of deposits. This will be explained in detail with reference to FIGS. 4a and 4b. Of course, a micromixer of other configuration that is commercially available can also be used. 11
  • FIGS. 4a and 4b show the molar mass distributions recorded by means of gel permeation chromatography, from which samples were taken after the tubular reactor 20 or from the discharge container 24.
  • the curves show the normalized frequency W (log M) over the molar masses of the solution polymers.
  • the solvent for the monomers or the initiator was tetrahydrofuran, the polymer concentration being between 5.61 and 5.64 g / l in the solvent.
  • the UV signal curve is shown with a solid line, while the R1 signal curve is dash-dotted, where R1 is the refractometer index or the refractive index.
  • the reaction is generally carried out in such a way that the distribution widths M n / M w in the polymers result from an ideally mixed free-radical polymerization, with the number average M n and the weight average M w of the molar mass distribution.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Polymerisation Methods In General (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
  • Physical Or Chemical Processes And Apparatus (AREA)

Abstract

Selon l'invention, deux partenaires de réaction (éduits) sont stockés dans des réservoirs (2, 3, 4 et 5) et sont conduits, au moyen de dispositifs de régulation et de dosage (6, 7), lesquels peuvent être des pompes de dosage, à un micromélangeur (18), sous surpression et en passant par des échangeurs thermiques (11, 12) chauffés. Dans les échangeurs thermiques (11, 12), les éduits sont chaque fois séparément chauffés de telle sorte que, lors du processus de mélange dans le micromélangeur (18), la température de réaction nécessaire est obtenue immédiatement. La polymérisation se fait dans un réacteur tubulaire (20), monté en aval, qui est constitué de tubes (21, 22, 23) montés en série.
PCT/EP1999/001734 1998-04-17 1999-03-17 Procede et dispositif pour la production en continu de polymeres WO1999054362A1 (fr)

Priority Applications (6)

Application Number Priority Date Filing Date Title
AU34135/99A AU3413599A (en) 1998-04-17 1999-03-17 Method and device for continuous production of polymers
AT99915632T ATE302796T1 (de) 1998-04-17 1999-03-17 Verfahren und vorrichtung zur kontinuierlichen herstellung von polymerisaten
JP2000544700A JP4410416B2 (ja) 1998-04-17 1999-03-17 ポリマーの連続製造方法および同装置
US09/673,156 US6555629B1 (en) 1998-04-17 1999-03-17 Method and device for continuous production of polymers
EP99915632A EP1086143B1 (fr) 1998-04-17 1999-03-17 Procede et dispositif pour la production en continu de polymeres
DE59912468T DE59912468D1 (de) 1998-04-17 1999-03-17 Verfahren und vorrichtung zur kontinuierlichen herstellung von polymerisaten

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19816886A DE19816886C2 (de) 1998-04-17 1998-04-17 Verfahren und Vorrichtung zur kontinuierlichen Herstellung von Polymerisaten
DE19816886.1 1998-04-17

Publications (1)

Publication Number Publication Date
WO1999054362A1 true WO1999054362A1 (fr) 1999-10-28

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Application Number Title Priority Date Filing Date
PCT/EP1999/001734 WO1999054362A1 (fr) 1998-04-17 1999-03-17 Procede et dispositif pour la production en continu de polymeres

Country Status (10)

Country Link
US (1) US6555629B1 (fr)
EP (1) EP1086143B1 (fr)
JP (1) JP4410416B2 (fr)
KR (1) KR100526914B1 (fr)
AR (1) AR023309A1 (fr)
AT (1) ATE302796T1 (fr)
AU (1) AU3413599A (fr)
DE (2) DE19816886C2 (fr)
ES (1) ES2248994T3 (fr)
WO (1) WO1999054362A1 (fr)

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JP2003523960A (ja) * 2000-01-14 2003-08-12 メルク パテント ゲゼルシャフト ミット ベシュレンクテル ハフトング カルボニル化合物と有機金属試薬の反応
DE102009019470A1 (de) 2008-05-02 2009-11-05 Basf Se Verfahren und Vorrichtung zur kontinuierlichen Polymerisation von kationisch polymerisierbaren Monomeren
EP2570180A1 (fr) 2011-09-15 2013-03-20 Bayer MaterialScience AG Procédé pour la polymérisation radicale continue au moyen de micro-réacteurs
US8546468B2 (en) 2008-05-02 2013-10-01 Basf Se Method and device for the continuous production of polymers by radical polymerization
US8969493B2 (en) 2008-05-02 2015-03-03 Basf Se Process and apparatus for continuously polymerizing cationically polymerizable monomers
CN110681327A (zh) * 2019-08-09 2020-01-14 中国科学院大连化学物理研究所 一种橡胶防焦剂ctp连续合成的微反应系统及方法
CN110681326A (zh) * 2019-08-09 2020-01-14 中国科学院大连化学物理研究所 一种橡胶防焦剂ctp合成的微反应系统及方法

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EP2915581B1 (fr) 2014-03-06 2017-07-12 Fluitec Invest AG Mélangeur statique
WO2016031752A1 (fr) * 2014-08-29 2016-03-03 国立研究開発法人海洋研究開発機構 Procédé de polymérisation radicalaire et appareil de réaction de polymérisation
CN109925975B (zh) * 2019-04-03 2020-09-01 中山华明泰科技股份有限公司 一种固体丙烯酸树脂管式自动反应装置
CN110774554A (zh) * 2019-12-13 2020-02-11 泰兴汤臣压克力有限公司 一种压克力板材一次反应挤出成型生产线

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JP2003523960A (ja) * 2000-01-14 2003-08-12 メルク パテント ゲゼルシャフト ミット ベシュレンクテル ハフトング カルボニル化合物と有機金属試薬の反応
DE102009019470A1 (de) 2008-05-02 2009-11-05 Basf Se Verfahren und Vorrichtung zur kontinuierlichen Polymerisation von kationisch polymerisierbaren Monomeren
US8546468B2 (en) 2008-05-02 2013-10-01 Basf Se Method and device for the continuous production of polymers by radical polymerization
US8969493B2 (en) 2008-05-02 2015-03-03 Basf Se Process and apparatus for continuously polymerizing cationically polymerizable monomers
US9108172B2 (en) 2008-05-02 2015-08-18 Basf Se Method and device for the continuous production of polymers by radical polymerization
EP2570180A1 (fr) 2011-09-15 2013-03-20 Bayer MaterialScience AG Procédé pour la polymérisation radicale continue au moyen de micro-réacteurs
CN110681327A (zh) * 2019-08-09 2020-01-14 中国科学院大连化学物理研究所 一种橡胶防焦剂ctp连续合成的微反应系统及方法
CN110681326A (zh) * 2019-08-09 2020-01-14 中国科学院大连化学物理研究所 一种橡胶防焦剂ctp合成的微反应系统及方法
CN110681327B (zh) * 2019-08-09 2021-07-23 中国科学院大连化学物理研究所 一种橡胶防焦剂ctp连续合成的微反应系统及方法
CN110681326B (zh) * 2019-08-09 2021-09-10 中国科学院大连化学物理研究所 一种橡胶防焦剂ctp合成的微反应系统及方法

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EP1086143A1 (fr) 2001-03-28
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DE19816886A1 (de) 1999-10-21
KR100526914B1 (ko) 2005-11-09
KR20010042764A (ko) 2001-05-25
JP2002512272A (ja) 2002-04-23
AU3413599A (en) 1999-11-08
ES2248994T3 (es) 2006-03-16
US6555629B1 (en) 2003-04-29
AR023309A1 (es) 2002-09-04
DE59912468D1 (de) 2005-09-29
ATE302796T1 (de) 2005-09-15
EP1086143B1 (fr) 2005-08-24

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